The present invention relates to a cement additive.
Generally, the surface of cement, mortar and concrete exposed to the air has the problem of gradual discoloration with time by the action of sunray, dust in the air, microorganisms etc. Accordingly, a method of reducing a water-cement ratio or using a water-permeable concrete form, or applying a water repellant onto the surface of concrete has been known as the method of suppressing discoloration.
One serious drawback of cement, mortar and concrete is that there easily occurs cracking on drying, which is attributable to high shrinkage of cement on drying. Accordingly, various reducing agents for reducing the shrinkage of cement compositions on drying have been proposed, and for example an adduct of alcohol with alkylene oxide (hereinafter abbreviated to AO) and an adduct of alkyl phenol with AO are known (e.g., U.S. Pat. No. 4,547,223 and JP-B 62-10947).
The conventional methods known to suppress discoloration of the surface of concrete are problematic in that special attention should be paid to the compounding method, the type of concrete form, and application of the water repellant.
Further, the conventional admixtures for reducing the shrinkage of cement, when added to concrete compositions, have the problem that the air content is easily influenced by the mixed concrete temperature, and if the air content is attempted to be regulated by an air-entraining admixture, a slight difference in the amount of the air-entraining admixture leads to a change in the air content in concrete, thus causing the problem that concrete containing a predetermined air content is hardly obtained.
The present inventors extensively studied a cement additive for preventing discoloration of the surface of concrete and a cement additive for easily regulating the air content in concrete, and as a result they arrived at the present invention.
That is, the present invention relates to [I] a cement additive composition for preventing discoloration of the surface of concrete, which comprises a cement additive (a) and a water-reducing admixture (b), wherein (a) comprises a mixture of compounds represented by the general formula (1):
R1O(AO)n1Hxe2x80x83xe2x80x83(1)
(wherein R1 is a C1-6 alkyl group, A is an ethylene group and/or a propylene group, and n1 is a number of 1 or more), and all the compounds wherein n1 is 2 to 6 are present in (a), the total content thereof (i.e. the content of the compounds wherein n1=2 to 6) is 40% by mass or more, the average of n1 is 1.5 to 10, the molecular weight distribution Mw/Mn is 1.05 or more, the Z average molecular weight Mz is 200 or more, and the ratio of (a):(b) by mass is (5 to 99.5):(95 to 0.5).
Further, the present invention relates to [II] a cement additive composition, which comprises a combination of (c) a compound or a mixture of two or more compounds represented by the general formula (2):
R2O(AO)n2Hxe2x80x83xe2x80x83(2)
(wherein R2 is hydrogen or a C1-6 alkyl group, A is an ethylene group and/or a propylene group, and n2 is a number of 1 to 10 on average) and (d) a compound or a mixture of two or more compounds represented by the general formula (3):
R3O(C3H6O)n3Hxe2x80x83xe2x80x83(3)
(wherein R3 is a C1-4 alkyl group, and n3 is a number on average of at least n2 +1 or of more than 10 to 100), the ratio of (c):(d) by mass being 100:(0.01 to 1).
Further, the present invention relates to [III] a concrete composition comprising a cement, any one of the above compositions in an amount of 0.5 to 10% based on the mass of the cement, water and an aggregate.
Further, the present invention relates to [IV] a concrete structure produced by hardening the concrete composition described above.
In the general formulae (1) and (2), the alkyl group R1 and R2 include a C1-6 straight-chain or branched alkyl group such as methyl, ethyl, n- and i-propyl, n-, i- and t-butyl, n-, i- and t-pentyl, and n- and i-hexyl. The alkyl group is preferably a C1-4 alkyl group, more preferably methyl and a straight-chain or branched butyl group.
In the general formula (1) and (2), A is an ethylene group and/or a propylene group, and AO is an oxyethylene group and/or an oxypropylene group, which are formed usually by adding ethylene oxide (hereinafter abbreviated to EO) and/or propylene oxide (hereinafter abbreviated to PO). If EO and PO are added in combination, they may be added in an arbitrary ratio (e.g., a molar ratio of from 1:99 to 99:1) in either a block or random form. When EO and PO are added in combination, block addition is preferable.
The additive (a) comprises a mixture of compounds represented by the general formula (1), in which the total content of the compounds wherein n1 is 2 to 6 is 40% or more, preferably 50% or more. In the general formula (1), n1 is a number of 1 or more, preferably a number of 1 to 10. The average of n1 is 1.5 to 10, preferably 2 to 7. In the foregoing and following description, % refers to % by mass unless otherwise specified.
The molecular weight distribution (Mw/Mn) of (a) [Mw and Mn refer respectively to weight-average and number-average molecular weights determined by gel permeation chromatography (GPC)] is 1.05 or more, preferably from 1.07 to 2. The Mz of (a) (determined by GPC) is 200 or more, preferably 250 to 1000. If (a) is outside of this range, it is not possible to achieve an excellent effect of preventing discoloration of the surface of concrete.
Insofar as the water-reducing admixture (b) used in the present invention is an admixture used generally for concrete, its composition is no limited. The water-reducing admixture (b) includes e.g. materials ordinarily used as air-entraining and water-reducing admixtures, high-range water-reducing admixtures, air-entraining and high-range water-reducing admixtures and superplasticizer [described in e.g. xe2x80x9cDeveloped Techniques of Concrete Admixturesxe2x80x9d published by C. M. C. Ltd. (1995)], and examples of such materials include lignin sulfonates (i.e. salts of alkali metals such as sodium and salts of alkaline earth metals such as calcium; this also applies to salts of the following compounds), naphthalin sulfonate formalin condensate salts (degree of condensation: 5 to 20), melamine sulfonate formalin condensate salts (degree of condensation: 5 to 20), polycarbonates [e.g. poly(meth)acrylate having a Mn of 5000 to 60,000, wherein (meth)acrylate means-acrylate and/or methacrylate, and this also applies throughout the description of the specification], aminosulfonate formalin condensate salts (degree of condensation: 2 to 20), and polycarboxylates [e.g. (meth)acrylic acid-(meth)acrylic acid polyoxyalkylene ester copolymer having a Mn of 10,000 to 600,000] containing polyether group (e.g. polyoxyalkylene group having a polymerization degree of 10 to 200, containing 2 and/or 3 carbon atoms in the alkylene group thereof), and these may also be used in combination. Preferable among these water-reducing admixtures are lignin sulfonates, naphthalin sulfonate formalin condensate salts, polycarboxylates and polyether group-containing polycarboxylates, more preferably lignin sulfonates and polyether group-containing polycarboxylates.
In the cement additive composition of the present invention [I], the ratio by mass of additive (a):water-reducing admixture (b) is (5 to 99.5):(95 to 0.5), preferably (20 to 99):(80 to 1). Here, the mass of (b) refers to the net weight of the water-reducing admixture as nonvolatile matter, that is, the mass from which a diluent such as water was removed. If (a) is less than 5%, the effect of preventing discoloration of the surface of concrete is not satisfactory, while if it exceeds 99.5%, the predetermined workability (particularly consistency) as concrete cannot be achieved.
Before preparation of the concrete composition, (a) and (b) may be previously mixed, or during preparation of the concrete composition, (a) and (b) may be separately added and mixed in the concrete composition.
In the general formula (2), n2 is a number of 1 to 10 on average. Preferably, it is a number of 1.5 to 10 on average, more preferably a number of 2 to 7 on average.
(c) is preferably the compound where R2 is an alkyl group, and (c) is particularly preferably the above-described (a). When (c) is the above-described (a), an excellent shrinkage-reducing effect is demonstrated.
In the general formula (3), R3 is a C1-4, straight-chain or branched alkyl group. Such group includes those exemplified for R1. The group is preferably a straight-chain or branched butyl group.
C3H6O is formed usually by addition of PO.
n3 is a number on average of at least n2+1 or of more than 10 to 100. n3 is preferably a number of 10 to 100 on average, more preferably a number of 10.1 to 95 on average, particularly preferably a number of 12 to 90 on average and most preferably a number of 20 to 80 on average. When n3 is 10 or less and simultaneously less than n2+1, the air content is increased upon addition of the composition to concrete, while if n3 exceeds 100, defoaming properties are increased so that concrete with the predetermined air content cannot be obtained.
In the cement additive composition of the present invention [II], the ratio by mass of (c):(d) is 100:(0.01 to 1), preferably 100:(0.05 to 0.8). When (d) is less than 0.01 or greater than 1, concrete having the predetermined air content is hardly obtainable, and the resulting composition is not sufficiently satisfactory for practical use.
The composition of the present invention [II] comprises two or more components comprising (c) and (d), and therefore two or more peak molecular weights are present in its molecular weight distribution curve. In the method of mixing (c) with (d), they may be previously mixed, or during preparation of the concrete composition, (c) and (d) may be separately added and mixed in the concrete composition.
In the cement additive composition of the present invention [II], a water-reducing admixture is preferably used in combination to further improve the shrinkage-reducing effect. The water-reducing admixture includes those described for the water-reducing admixture (b), and preferable examples thereof are also described therein.
The ratio by mass of the total of (c) and (d):(b) is preferably (5 to 99.5):(95 to 0.5), more preferably (20 to 99):(80 to 1). When the total of (c) and (d) is in the range of 5 to 99.5%, a sufficient shrinkage-preventing effect is demonstrated, and there is no problem with workability (particularly consistency) as concrete.
Cement to which the additive composition of the present invention is added is conventional hydraulic cement. That is, mention is made of various kinds of Portland cement such as normal Portland cement (high-early-strength Portland cement, moderate-heat Portland cement etc.), blended cement (Portland blast-furnace slag cement, Portland fly-ash cement etc.).
The amount of the cement additive composition of the present invention [I] or [II] added to the concrete composition of the present invention [III] is varied depending on the number of carbon atoms in the alkyl group of the compound represented by the general formula (1) or (2), but its amount is usually 0.5 to 10%, preferably 1 to 8% relative to the cement. If the amount of the cement additive composition used is less than 0.5%, the resulting concrete composition is poor in the effect of preventing discoloration of the surface of concrete or in the effect of reducing shrinkage, while if it exceeds 10%, the resulting concrete composition is practically not satisfactory because the strength of concrete is about ⅔ or less relative to the strength of concrete to which the composition was not added. Further, the amount of the water-reducing admixture (b) in the present invention [II] is preferably 5% or less, more preferably 0.05 to 4% relative to the cement. If its amount is 5% or less, the influence thereof on the strength of concrete is low.
The means of adding the additive composition may be the same as for conventional concrete admixtures. For example, a suitable amount of the additive composition may be admixed with water to be admixed, or may be added to once mixed fresh concrete. Alternatively, the additive composition may be allowed to penetrate into the surface layer of a cement product.
The additive composition of the present invention is not limited by the admixture used. That is, the additive composition can be used in combination with conventional air-entraining admixture (AE admixture) used in concrete, such as resinates and surfactants (polyoxyethylene alkyl aryl ethers etc.); known expansive additives based on calcium sulfoaluminate or quicklime; known accelerators such as calcium chloride, triethanolamine etc.; known retarders such as polyhydric alcohols, sugars, oxycarboxylates etc.; known corrosion inhibitors such as nitrites etc.; and other known admixtures for mortar or concrete. These admixtures are described in xe2x80x9cDeveloped Techniques of Concrete Admixturesxe2x80x9d supra.
In the composition of the present invention [III], the amount of the admixture used is varied depending on the type of the admixture but may be in the ordinarily used range. For example, the amount of the air-entraining admixture (AE admixture) is usually 0.1% or less, preferably 0.001 to 0.06% relative to the cement.
The cement additive composition of the present invention can be used in combination with a shrinkage-reducing admixture [described in e.g. xe2x80x9cDeveloped Techniques of Concrete Admixturesxe2x80x9d supra] such as phenol or alkyl (C1-3) phenol AO (EO and/or PO) adduct (number of moles of AO added: 1 to 10) and polypropylene glycol (number average molecular weight: 500 to 1500) as a component other than those in the cement additive composition of the present invention.
The amount of the shrinkage-reducing admixture other than the components in the cement additive composition of the present invention [I] or [II] is preferably 50% or less based on the additive composition of the present invention. In the case of 50% or less, the effect of preventing deterioration of the surface of concrete or the easiness of regulating the air content in concrete is not deteriorated.
The total amount of the cement additive other than the cement additive composition of the present invention and the water-reducing admixture (b) in the present invention is preferably 5% or less, more preferably 0.01 to 4% relative to the cement.
Water used in the concrete composition of the present invention [III] is water prescribed in Document 9 attached to Japanese Industrial Standard (JIS) A 5308, and such water includes tap water, other water (water in rivers, lakes and marshes, well-water, etc.), recovered water etc.
In the composition of the present invention, water is used preferably in such an amount that the water/cement ratio (i.e. % of water relative to cement) becomes 65 to 20%. In the case of 65% or less, sufficient concrete strength can be achieved, and in the case of 20% or more, good workability (particularly consistency) can be achieved by use of the water-reducing admixture.
In the concrete composition of the present invention [III], the aggregate includes fine aggregate and coarse aggregate. The fine aggregate used includes the aggregate prescribed in Document 1 attached to JIS A 5308. Such aggregate includes river sand, land sand, pit sand, sea sand, crushed sand etc.
The fine aggregate is compounded in an amount of 500 to 1200 kg per m3 of concrete. By compounding this amount of fine aggregate, the product is excellent in both concrete strength and workability (particularly consistency).
The coarse aggregate used in the concrete composition of the present invention [III] includes the aggregate prescribed in Document 1 attached to JIS A 5308. Such aggregate includes river gravel, land gravel, pit gravel, crushed stone etc.
The coarse aggregate is compounded preferably in an amount of 500 to 1200 kg per m3 of concrete. By compounding this amount of coarse aggregate, the product is excellent in both concrete strength and workability (particularly consistency).
In the composition of the present invention [III], the proportion of fine aggregate (sand-total aggregate ratio) is preferably 35 to 70% by volume. The proportion of fine aggregate indicates the volume % of fine aggregate relative to the total amount of fine aggregate and coarse aggregate, and the optimum proportion of fine aggregate is varied depending on the type and shape of aggregate used, and usually the proportion of fine aggregate is determined in a test such that the unit amount of water becomes minimized within a range in which predetermined workability (particularly consistency) is achieved.
The concrete structure of the present invention [IV] is obtained by hardening the concrete composition of the present invention [III], and the method of hardening thereof is not particularly limited and may be a conventional method. The hardening or curing method may be air drying curing, humid air curing, underwater curing, accelerated curing by heating (steam curing, autoclave curing) and these can also be used in combination.
In the concrete structure of the present invention [IV] wherein the cement additive composition of the present invention [I] was added to cement in an amount of 2.25%, the reduction in lightness of the surface of the concrete structure after 5 years is usually in the range of 2 to 4, as compared with a usual reduction of 9 or more in concrete to which the composition was not added, thus indicating a superior effect of preventing discoloration of the surface of the concrete structure.
Further, in the case of the concrete structure wherein the cement additive composition of the present invention [II] was added to cement in an amount of 2.25% while the air-entraining admixture (AE admixture) was added to cement in a varying amount from 0.002% to 0.01%, an air content therein is usually in the range of 2 to 7% by volume, as compared with an air content is sometimes either less than 2% or higher than 8% by volume upon addition of the conventional shrinkage-reducing agent, thus indicating less influence of the varying amount of the AE admixture on air entrainment thereby achieving easy regulation of the air content in concrete.
Best Mode for Carrying out the Invention
Hereinafter, the present invention is described in more detail by reference to the Examples, which are not intended to limit the present invention. In the Examples, the term xe2x80x9cpartsxe2x80x9d refers to xe2x80x9cparts by massxe2x80x9d.
In a test method on the effect of preventing discoloration, a test specimen having a thickness of 15 cm, a height of 100 cm and a width of 50 cm assumed to be used as a wall member was prepared for each compounding condition. 7 days after, the test specimen was removed from a concrete form and subjected to air-curing at room temperature for 28 days. Thereafter, the test specimen was installed outdoors in Tokyo with its poured surface up and its 50 cmxc3x97100 cm surface toward north and south. As the concrete form, a urethane-coated plywood was used.
The color of the surface of each test specimen was measured by an L*a*b* color-specifying meter (JIS Z 8729) using a contact-type colorimetric color difference meter (Minolta Co., Ltd.), and the effect of preventing discoloration was evaluated in terms of lightness (L value). As regards the measurement position, color measurement was conducted at 10 sites in total apart by 5 cm, 15 cm, 25 cm, 35 cm and 45 cm from the left-hand side on the horizontal line apart by 15 cm and 30 cm from the upper end of the north surface. The results are expressed in terms of the average of L values at the 10 sites. The measurement was conducted at the start of the exposure test and after 5 years of exposure, respectively.
Further, the slump was measured according to JIS A 1101, the air content in concrete was measured according to JIS A 1128 and the degree of shrinkage was measured according to JIS A 1129. A xcfx8610xc3x9720 cm concrete sample was prepared according to JIS A 1132 and subjected to underwater curing at 20xc2x0 C. for 28 days and measured compressive strength according to JIS A 1108.
The raw materials of concrete used in the Examples and Comparative Examples are as follows.
In the following, Me is methyl alcohol, n-Bu is n-butyl alcohol, i-Bu is i-butyl alcohol, and the value in the parenthesis indicates the average number of moles of units added; for example Me-EO (1)-PO (4) indicates a methyl alcohol-ethylene oxide (average number of moles of EO added: 1)-propylene oxide (average number of moles of PO added: 4) block adduct.
Cement Additive (a) in the Present Invention [I]
The Mw, Mn and Mz in Table 1 were measured under the following conditions:
Measuring unit:
GPC system [HLC-8120GPC] manufactured by Tosoh.
Eluent:
Type, tetrahydrofuran
Flow rate, 0.6 (ml/min.)
Columns:
TSK gel Super H2000
+TSK gel Super H3000
+TSK gel Super H4000
Cement Additive Compositions (C) of the Present Invention [II]
C-1: A composition of 100 parts of Me-PO (3) and 0.05 part of n-Bu-PO (30)
C-2: A composition of 100 parts of n-Bu-EO (2) and 0.1 part of n-Bu-PO (30)
C-3: A composition of 100 parts of n-Bu-PO (2)-EO (2) and 0.5 part of i-Bu-PO (50)
C-4: A composition of 100 parts of Me-EO (1)-PO (4) and 0.05 part of n-Bu-PO (30)
Comparative Cement Additives or Cement Additive Compositions (R)
R-3: Me-PO (3)
R-4: n-Bu-PO (2)-EO (2)
R-5: A composition of 100 parts of n-Bu-PO (2)-EO (2) and 3 parts of n-Bu-PO (30)
R-6: A composition of 100 parts of n-Bu-PO (2)-EO (2) and 0.1 part of n-Bu-PO (120)
R-7: Me-EO (1)-PO (4)
Water-Reducing Admixtures (b)
b-1: Air-entraining and water-reducing admixture (Pozzolith No. 70, produced by NMB)
b-2: Air-entraining and high-range water-reducing admixture (Rheobuild SP-8S, produced by NMB)
The above xe2x80x9cPozzolithxe2x80x9d and xe2x80x9cRheobuildxe2x80x9d are registered trademarks. xe2x80x9cMicroairxe2x80x9d in the AE admixture (H) below is also a registered trademark.
Cement (D)
D-1: Normal Portland cement (produced by Taiheiyo Cement Corp.)
Water (E)
E-1: Tap water
Fine Aggregate (F)
F-1: Crushed sand (specific gravity: 2.60, fineness modulus=2.80, produced by Chichibu Kogyo Co., Ltd.)
Coarse Aggregate (G)
G-1: Crushed stone (2005, specific gravity of 2.60, produced by Chichibu Kogyo Co., Ltd.)
AE Admixture (H)
H-1: Microair 303A produced by NMB